The reaction of alkylcobaloxime [Co(dmgH)2(CH2CH3)(py)] (1) (dmgH = the anion of dimethyl-glyoxime) with KSH in water solution resulted in the selective displacement of the pyridine axial ligand affording the derivative K[Co(dmgH)2(CH2CH3)(SH)] (2). An 1H-1H EXSY experiment revealed that the substitution is reversible and occurs in a slow exchange regime. Attempts to grow crystals of the HS- adduct led to isolation of a rare example of the unexpected trisulfido-bridged dinuclear complex K2[Co2(dmgH)2(CH2CH3)2(μ-S3)]. It was shown that the glyoximato ligands provided the metal centre with a coordination environment quite robust to prevent decomposition and constitute a suitable platform for developing the chemistry of organometallic complexes bearing hydrogensulfido or oligosulfido ligands.

Organometallic sulfur complexes: reactivity of the hydrogen sulfide anion with cobaloximes

BERTOLASI, Valerio;
2015

Abstract

The reaction of alkylcobaloxime [Co(dmgH)2(CH2CH3)(py)] (1) (dmgH = the anion of dimethyl-glyoxime) with KSH in water solution resulted in the selective displacement of the pyridine axial ligand affording the derivative K[Co(dmgH)2(CH2CH3)(SH)] (2). An 1H-1H EXSY experiment revealed that the substitution is reversible and occurs in a slow exchange regime. Attempts to grow crystals of the HS- adduct led to isolation of a rare example of the unexpected trisulfido-bridged dinuclear complex K2[Co2(dmgH)2(CH2CH3)2(μ-S3)]. It was shown that the glyoximato ligands provided the metal centre with a coordination environment quite robust to prevent decomposition and constitute a suitable platform for developing the chemistry of organometallic complexes bearing hydrogensulfido or oligosulfido ligands.
2015
Strianese, Maria; Mirra, Silvia; Bertolasi, Valerio; Milione, Stefano; Pellecchia, Claudio
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11392/2336676
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